Process for the preparation of ethers

Abstract

A process for the preparation of ethers is described wherein at least one alcohol is contacted in the presence of carbon monoxide with a catalyst system having the general formula:

b_x Me[Me'(CO)_a (L)_b ]₂

and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 16 to about 100 wherein b is a lewis base capable of coordinating with a group iia metal; Me is a group iia metal, preferably magnesium; Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of the Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula:

(C₄ H₈ O)₄ Mg[Mn(CO)₄ P(C₄ H₉)₃ ]₂

and a cocatalyst comprising methyl iodide.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 166,615, filed July 27, 1971, now abandoned which in turn is a continuation-in-part of U.S. Ser. No. 51,669, filed July 1, 1970, now abandoned. This application is also related to U.S. Ser. No. 419,367, filed Nov. 27, 1973, now U.S. Pat. No. 3,968,128, which is a continuation-in-part of U.S. Ser. No. 51,669.

FIELD OF THE INVENTION

The present invention is directed to a process for the preparation of ethers wherein at least one alcohol is contacted in the presence of carbon monoxide with a catalyst system having the general formula:

B_x Me[Me'(CO)_a (L)_b ]₂

and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 16 to about 100, wherein B is a Lewis base capable of coordinating with a Group IIA metal; Me is a Group IIA metal, preferably magnesium; Me' is a transition metal selected from the group consisting of metals of Group VIB, VIIB and VIII of the Periodic Table of Elements; L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with the transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5; b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. A typical preferred catalyst system is represented by the general formula:

(C₄ H₈ O)₄ Mg[Mn(CO)₃ P(C₄ H₉)₃ ]₂

and a cocatalyst comprising methyl iodide in cocatalyst to catalyst molar ratio ranging from 16 to 100.

DESCRIPTION OF THE PRIOR ART

Carbonylation processes wherein alcohols, ethers, esters and halogen-containing compounds are contacted with carbon monoxide at high temperatures and pressures are known in the art. The catalysts which have been utilized in the prior art processes are generally Group VIII metals, e.g., cobalt, nickel and iron salts which under the carbonylation reaction conditions will be converted to carbonyl compounds.

In U.S. Pat. No. 2,650,646 there is disclosed a process for carbonylating methanol by contacting methanol with carbon monoxide in the presence of a nickel carbonyl compound and methyl iodide. This patent also indicates that the volatility of the nickel carbonyl and methyl iodide pose a problem to the skilled artisan. For example, it is known that catalyst loss due to volatility is a severe problem when employing any of the simple carbonyl derivatives of cobalt, nickel and iron.

In U.S. Pat. No. 2,710,878 a further problem in the process for the conversion of an alcohol to an organic acid in the presence of a catalyst system comprising a nickel or a cobalt salt and a halide cocatalyst is disclosed, i.e., the necessary high temperatures, pressures and acidic reaction mixtures, cause extreme corrosion of the usual reactor equipment.

U.S. Pat. Nos. 2,898,366 and 2,898,367 disclose a process wherein lower aliphatic alcohols are reacted with carbon monoxide in the presence of a catalyst system comprising a nickel salt and iodine and/or hydrogen iodine at temperatures of at least 325°C and pressures upwards of 3,000 psi.

U.S. Pat. No. 3,014,962 discloses a more active catalyst system wherein a chelating compound is added to the iron, cobalt and nickel salt catalyst and halogen containing cocatalyst of the prior art processes. This catalyst system produces carboxylic acids as the major product.

U.S. Pat. Nos. 2,734,193 and 3,505,408 describe carbonylation catalyst systems wherein the nickel or cobalt is in the anion of a complex salt. These systems, although useful in the hydroformylation of olefins, are not very active alcohol carbonylation catalysts.

The covalent nature of bonds between main group elements and transition metals has been well established by numerous chemical, structural, and spectroscopic investigations. Many compounds are known in which a main Group IVA or IIB metal is covalently bonded to a transition metal. Cases in which a transition metal is bonded to an element of main Group IIA or IIIA are, by contrast, few in number. Group IA transition metal compounds are known but are essentially ionic and are generally not isolated and are handled as solutions in polar solvents.

It is generally found that the covalent nature of a main Group IIIA or main Group IVA metal bonded to a transition metal decreases as one moves from Group IVA to Group IIA or ascends either respective group. This trend in covalent bonding is responsible for the failure of the early numbers of Group IIIA to form easily insolatable compounds with transition metals (the transition metal anion is the seat of reactivity and is readily attacked by electrophiles).

Group IIA-transition metal compounds have been described in two instances, but in both cases hereafter noted, the proposed composition and structure was incorrectly postulated. Von W. Hieber et al., Zeitschrift fur anorganische und allgemeine Chemie, 125-143, (March 1962) described the reaction of a dimeric manganese carbonyl complex with magnesium amalgam in the presence of tetrahydrofuran to give the bis-tetrahydrofuran adduct of a magnesium-manganese carbonyl complex. This product is not produced under the reaction conditions described; instead the tetrakis adduct is obtained in quantitative yield. Furthermore, Hieber et al, only teach a method for preparing the complex (C₄ H₈ O)₂ Mg[Mn(CO₄)P(C₆ H₅)₃ ]₂. The stability of this complex is largely due to the stabilizing effect of the phosphine ligand P(C₆ H₅)₃. The ability of P(C₆ H₅)₃ to impart thermal stability to carbonyl complexes is well documented in the literature.

Burlitch and Ulmer, Journal of Organometallic Chemistry, 19, 21-23 (1969) described the preparation of halides of magnesium transition metal carbonyl complexes (transition metal carbonyl Grignard reagents) by the reaction of the transition metal carbonyl halide with magnesium in the presence of tetrahydrofuran. Burlitch and Ulmer did not isolate these products, but inferred that they existed by further reactions of the unisolated complex. The applicant has found that halide derivatives of magnesium-transition metal carbonyl complexes cannot be prepared.

Group IIA-transition metal compounds would be expected to be more ionic in nature than the corresponding IIB derivatives. A balance between covalent and ionic bonding contributions to the hetero metal-metal bond is needed to insure reasonable solubility in organic solvents. Hydrocarbon solubility is, of course, a necessary for use of the Group IIA-transition metal compound as a homogeneous catalyst for hydrogenation, polymerization, dimerization, carbonylation and hydroformylation reactions.

DISCOVERY OF THE INVENTION

It has been unexpectedly found that a transition metal carbonyl can be reacted with a metal chosen from Group IIA of the Periodic Table of the Elements in the presence of a Lewis base, to give novel compounds, wherein the transition metal is bonded to the Group IIA metal. This reaction is effected, preferably, by the reaction of an amalgam of the Group IIA metal with a dimeric transition metal carbonyl complex.

It has also been discovered that these novel compounds are effective catalysts for the production of acids, esters, ethers and acyl halides.

More particularly, it has been discovered that these novel compounds provide an excellent catalyst system when used in combination with a halogen containing compound as a cocatalyst to produce ethers from alcohols.

SUMMARY OF THE INVENTION

One aspect of the present invention is directed to an improved ether-forming process comprising contacting a compound of the general formula:

R -- X

wherein R represents a hydrocarbyl radical and X represents a hydroxyl or bisulfide radical (SH) with a novel catalyst system, said novel catalyst system comprising a Group IIA metal-transition metal carbonyl catalyst wherein the transition metal is bonded to the Group IIA metal in the presence of carbon monoxide and a halogen containing cocatalyst preferably an iodine containing cocatalyst and more preferably an iodine containing compound selected from the group consisting of I₂, HI and organo iodides. An especially preferred iodine containing cocatalyst is methyl iodide. Preferably X represents a hydroxyl radical and thus alcohols are the preferred reactants.

Another aspect of the present invention is directed to an improved process comprising contacting an olefinic compound and an alcohol with a carbon monoxide containing gas in the presence of a novel catalyst system, said novel catalyst system comprising a Group IIA metal-transition metal carbonyl catalyst wherein the transition metal is bonded to the Group IIA metal and having the general formula:

B_x Me(M)₂

wherein B is a Lewis base; x is an integer ranging from 1 to 4; Me is a Group IIA metal; and M is a transition metal carbonyl or substituted transition metal carbonyl complex.

The processes of the present invention provide an improved means for obtaining carboxylic acid esters and ethers. By use of the improved catalyst system of the instant invention, the following improvements are noted:

(1) Lower temperatures and pressures may be used.

(2) Either ethers or esters may be selectively produced by varying the ratio of the catalyst and cocatalyst.

(3) The catalyst system is nonvolatile.

(4) The reaction mixtures are noncorrosive.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A preferred aspect of the present invention relates to a process for the preparation of ethers which comprises contacting at least one alcohol at a temperature in the range from about 200° to about 400°C with carbon monoxide at a carbon monoxide partial pressure in the range from about 200 to about 1000 psig in the presence of a catalyst system having the general formula:

B_x Me[Me'(CO)_a (L)_b ]₂

and a cocatalyst comprising halogen containing compounds in a cocatalyst to catalyst molar ratio ranging from about 16 to about 100, wherein B is a Lewis base capable of coordinating with a Group IIA metal, Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB and VIII of the Periodic Table of Elements, Me is a Group IIA metal, L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with said transition metal, x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less. The cocatalyst is preferably an iodine containing compound, particularly an iodine containing compound selected from the group consisting of I₂, HI and organo iodides. An especially preferred iodine containing compound is methyl iodide.

This process is capable of producing ethers in high yield and good selectivity at low temperatures and pressures. These advantages are attributed to the use of the novel catalyst compounds wherein the transition metal is bonded to the Group IIA metal.

The alcohols used as the preferred starting materials in the instant process include the hydrocarbyl alcohols such as alkanols and aralkanols which contain from one to about 20 carbon atoms, preferably from one to about 8 carbon atoms, and more preferably one to 4 carbon atoms. Preferred alcohols include methanol, ethanol, propanol, isopropanol, butanol, and mixtures thereof, methanol being particularly preferred.

In general, the process of the instant invention will take place at a temperature of from 100° to 400°C and at a carbon monoxide partial pressure ranging from about 200 to about 10,000 psig, depending on the preponderance of products desired, i.e., ethers or esters.

The alcohol reactant may be contacted with the carbon monoxide containing gas neat or dissolved in a solvent. Solvents which can be utilized in the process of the instant invention include benzene, toluene, tetrahydrofuran, ethyl ether, etc.

It is obvious that the carbon monoxide does not have to be added to the reaction product in pure form. It may be combined with various inert gases. For example, an especially economical source of carbon monoxide, i.e., from partical combustion or steam reforming processes, will contain CO₂ and hydrogen as well as carbon monoxide. This mixture can be used in the process of the instant invention.

The molar ratio of the catalyst system to the alcohol reactant may vary from 0.0001 to 0.1, preferably 0.001 to 0.1. The molar ratio of catalyst to cocatalyst may vary from 1 to 100, depending on the preponderance of product, i.e., ether or ester if one wishes to obtain as explained below.

The reaction time will be apparent to the skilled artisan and he may choose his reaction time based on the temperatures and pressures utilized.

The instant process is capable of being run batchwise or continuously. The process of the instant invention will usually be run in reactors known to the skilled artisan and includes, because of the oxygen sensitivity of the catalyst system of the instant invention, provisions for the exclusion of oxygen. It is noted that special reactor lines are not needed in the process of the instant invention because of the relatively low temperatures and pressures utilized and the noncorrosive nature of the catalyst.

In practicing the process of the instant invention, a hydrocarbyl alkanol having from 1 to 20 carbon atoms is contacted with carbon monoxide in the presence of the novel catalyst system at an elevated temperature and pressure for a time sufficient to convert at least some of the alcohol to the ether product. The composition of the final reaction product, i.e., ester or ether, is controlled by varying the reaction conditions including the cocatalyst to catalyst ratio. It has been discovered that ester formation is favored by increased carbon monoxide partial pressures and low cocatalyst to catalyst ratios, whereas ether formation is favored by relatively high ratios of cocatalyst to catalyst, high temperatures and low carbon monoxide pressures.

For example, a carbon monoxide pressure ranging from about 200 to 1000 psig, preferably 300 to 1000 psig, favors ether formation, whereas carbon monoxide pressures ranging from 1000 to 4000 psig favors ester formation. A temperature ranging from 150° to 400°C, preferably 200° to 400°C favors ether formation whereas temperatures ranging from 100° to 200°C favors ester formation. A cocatalyst to catalyst molar ratio range of from 16 to 100 favors ether formation, where a cocatalyst to catalyst molar ratio of from 1 to 16 favors ester formation.

It will be noted that the process of the instant invention is capable of being operated at low temperatures and pressures compared to the prior art processes and therefore represents a significant advantage. Also, increased selectivity to ether (when desirable), high catalyst stability, and noncorrosive reaction mixture are important improvements of the present process over the known-in-the-art carbonylation processes.

The process of the instant invention is also applicable to the production of unsymmetrical ethers and esters. For example, a mixture of methanol and isopropanol when reacted under conditions to yield ethers will give the following products: dimethyl ether, diisopropyl ether and methyl isopropyl ether. When the reaction is run under conditions so that an ester product will be dominant, i.e., methyl acetate, isopropyl acetate, and small amounts of methyl propionate and isopropyl propionate are produced. In general, in a process for producing esters, the lower alcohol will preferentially form the acyl function. Of course, the reaction conditions can be adjusted so that mixtures comprising both esters and ethers are formed at once. The formation of unsymmetrical lower alkyl ethers is especially important since these products have utility as gasoline octane improvers.

The Novel Catalyst Compounds

The novel catalyst compounds used in the ether production process of the present invention are preferably those represented by the general formula:

B_x Me[Me'(CO)_a (L)_b ]₂

B is a Lewis base capable of coordinating with a Group IIA metal, such as magnesium, through a lone pair of electrons thereby stabilizing the Group IIA metal-transition metal complexes. The Lewis base is preferably a member selected from the group consisting of:

1. Organic nitrogen bases.

2. Ethers; and

3. Ketones.

Me is a Group IIA metal, preferably magnesium;

Me' is a transition metal selected from the group consisting of Groups VIB, VIIB and VIII of the Periodic Table of the Elements (examples of the useful transition metals include molybdenum manganese, tungsten, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum; molybdenum, manganese and cobalt being most preferred);

L is a uni- or polydentate ligand capable of coordinating with the transition metal or a hydrocarbon residue;

x is a positive integer ranging from 1 to 4;

a is a positive integer ranging from 1 to 5;

b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less.

The organic nitrogen bases (B) useful as Lewis bases to coordinate with the Group IIA metal and selected from the group consisting of:

(a) monofunctional nitrogenous bases represented by the general formulae: ##STR1## wherein R, R' and R" are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals;

(b) polyfunctional nitrogenous bases represented by the general formula: ##STR2## wherein R"' and Rⁱv are selected from the group consisting of hydrogen and C₁ to C₁0 hydrocarbyl radicals, R₁ is selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals, Z is selected from the group consisting of radicals represented by the general formulae: ##STR3## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals and y is a positive integer ranging from 1 to 3; and

(c) heteroring nitrogenous bases selected from the group consisting of piperazine, pyrrolidine, pyridine and substituted pyridines of the formula: ##STR4## wherein R₆ is a C₁ to C₁0 hydrocarbyl radical and z is an integer from 0 to 5.

Preferred examples of organic nitrogen bases which are within the above description include: monofunctional nitrogenous bases:

Ammonia

Methylamine

Dimethylamine

Trimethylamine

Triethylamine

Methyl diethylamine

Pyridine

N-decyl pyridine

N-decyl pyridine

Aniline

Bifunctional nitrogenous bases

2,2-bipyridyl

1,10-phenanthroline

Ethylene diamine

Tetramethylenediamine

1,3-propylene diamine

Tetrafunctional nitrogenous bases ##STR5## Hexamethyltriethylenetetramine Triethylenetetramine

The ethers useful as Lewis bases (B) to coordinate with the Group IIA metal are selected from the group consisting of:

(a) monofunctional ethers represented by the general formula:

R -- O -- R'

wherein R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0, C₇ to C₁0 alkaryl and aralkyl radicals.

(b) polyfunctional ethers represented by the general formulae: ##STR6## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals, R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals and y is a positive integer of from 1 to 3; and

(c) cyclic ethers selected from the group consisting of tetrahydrofuran and dioxane.

Examples of mono-, bi- and tetrafunctional oxygenated ethers which can coordinate to Group IIA metals, e.g., magnesium through a lone pair of electrons thereby stabilizing the Group IIA metal-transition metal complexes are listed below.

Monofunctional ethers

Tetrahydrofuran

Tetrahydropyran

Dioxane

Diethyl ether

Dipropyl ether

Methyl ethyl ether

Dicyclohexyl ether

Diphenyl ether

Methylphenyl ether

Difunctional ethers

Ch₃ och₂ ch₂ och₃ (glyme)

Ch₃ ch₂ och₂ ch₂ och₂ ch₃ (1,2-di-ethoxyethane)

C₃ h₇ och₂ ch₂ och₂ ch₃ (1-propoxy-2-ethoxyethane)

C₆ h₅ och₂ ch₂ oc₆ h₅ (1,2-diphenoxy-ethane)

Tetrafunctional ethers

Ch₃ och₂ ch₂ och₂ ch₂ och₂ ch₂ och₃ (triglyme)

Ketones useful as Lewis bases (B) to coordinate with the Group IIA metal are represented by the general formula: ##STR7## wherein R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals, R₁ and R₂ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals and z is an integer of from 0 to 3.

Examples of useful ketones are listed below:

Acetone

Methyl ethyl ketone

Dicyclohexyl ketone

Methyl cyclohexyl ketone

Diphenyl ketone

Cyclohexanone

Methyl phenyl ketone

Acetylacetone

1,2-cyclohexandione

1,3-cyclohexandione and

2,4,6,8-n-nonatetraone.

L is preferably selected from compounds of the group having the following general formulae: ##STR8## wherein R, R', R" and R'" and hydrocarbyl radicals independently selected from the group consisting of hydrogen, C₁ to C₂0 alkyl, C₃ to C₂0 cycloalkyl, C₆ to C₂0 aryl and C₇ to C₂0 aralkyl and alkaryl radicals and X is a member selected from the group consisting of N, P, As and Sb, with P being preferred.

Thus, compounds within the scope of this definition include:

Cyclopentadiene

Methyl cyclopentadiene

Ethyl cyclopentadiene

Butyl cyclopentadiene

Phosphine

Trimethyl phosphine

Triethyl phosphine

Tributyl phosphine

Methyl diphenyl phosphine

Triphenyl phosphine

Butyl diphenyl phosphine

Triethylamine

Triethylarsine, and

Triethylstibine.

L may also represent more than one ligand independently selected from the above group. For example, in the compound

[C₄ H₈ O]₄ Mg[Mo(CO)₂ (PCH₃ (C₆ H₅)₂ C₅ H₅ ]₂

wherein a would equal 2, and L would equal methyl diphenyl phosphine and cyclopentadiene.

The above-mentioned novel compounds can be prepared by any of four methods:

1. A slight excess of MeX₂ (wherein Me is a Group IIA metal and X is Cl, Br or I, preferably Cl or Br) dissolved in tetrahydrofuran (THF) can be added to the Na derivative of the transition metal carbonyl complex, with agitation. After the reaction is complete, the crude reaction mixture is filtered to remove the insoluble NaX formed. The filtrate is concentrated with reduced pressure and the magnesium transition metal compound is precipitated by adding n-pentane. The solid product is purified by recrystallization from benzene. Examples of some sodium derivatives of transition metal carbonyl complexes include:

Na^.sym. [Fe(CO)₂ (C₅ H₅)]^.crclbar.

na^.sym. [Mo(CO)₃ (C₅ H₅)]^.crclbar.

na^.sym. [Co(CO)₄ ]^.crclbar.

na^.sym. [Co(CO)₃ (P(nC₄ H₉)₃))]^.crclbar.

examples of reaction pathways:

MgCl₂ + 2Na[Co(CO)₃ P(nC₄ H₉)₃ ] ^THF (THF)₄ Mg[Co(CO)₃ P (C₄ H₉)₃ ] + 2NaCl

BeCl₂ + 2NaCo(CO)₄ ^THF (THF)₂ Be(Co(CO)₄)₂ + 2NaCl

(2) A solution of a transition metal carbonyl derivative of Hg is reacted with the Group IIA metal. The crude reaction mixture is filtered to remove the free mercury formed by the metal exchange reaction. The magnesium transition metal compound is isolated from the filtrate as in (1) above. Examples of some Hg derivatives of transition metal carbonyl complexes include:

Hg(Fe(CO)₂ C₅ H₅)₂

hg(Co(CO)₄)₂

hg(Co(CO)₃ P(C₆ H₅)₃)₂

hg(Mo(CO)₃ C₅ H₅)₂

typical reaction pathway: ##STR9##

(3) The same procedure as in (2), except that a transition metal carbonyl halide compound is used instead of the mercury derivative. The Group IIA halide formed is removed by filtration. Examples of some transition metal carbonyl halides include:

(C₅ H₅)Fe(CO)₂ I, (C₅ H₅)Fe(CO)₂ Br

(C₅ H₅)Mo(CO)₃ I

(c₅ h₅)mo(P(nC₄ H₉)₃)(CO)₂ I

(c₅ h₅)ni(CO)l

((C₆ H₅)₃ P)₂ Rh(CO)CI

(co)₅ mnBr

Typical reaction pathway:

2(C₅ H₅)Fe(CO)₂ I + 2Mg ^THF (THF)₂ Mg(Fe(CO)₂ C₅ H₅)₂ + MgI₂

(4) an amalgam of the Group IIA metal is reacted with a dimeric metal carbonyl complex yielding the above mentioned novel compounds. Examples of some dimeric metal carbonyl complexes include:

(Fe(CO)₂ (C₅ H₅))₂

(mo(CO)₃ (C₅ H₅))₂

((c₅ h₅)ni(CO))₂

co₂ (CO)₈

co₂ (CO)₆ (P(nC₄ H₉)₃)₂

mn₂ (CO)₁0

(w(co)₃ c₅ h₅)₂

typical reaction pathway: ##STR10##

All of the above procedures are carried out under an inert atmosphere, generally nitrogen. The reaction temperature range varies from -40° C. to 200°C, preferably between 0°C and 120°C, and most preferably between room temperature and 100°C

The reaction of the Group IIA metal (and also the amalgam as shown above) and the transition metal carbonyl complex normally takes place in a solvent. Inert solvents such as benzene, toluene, n-pentane, etc., can be used as long as there is also present enough Lewis base such as pyridine, tetrahydrofuran, etc., to coordinate with the Group IIA metal, as noted above. Preferably, the reaction is carried out in the presence of a substantial excess of the Lewis base, and if the reactants are soluble in the Lewis base, the solvent can consist entirely of the Lewis base. It should be noted that the solubility of the Group IIA-transition metal carbonyl complex in hydrocarbon solvents is dependent on the nature of the Lewis base adduct. For example, in benzene the solubility of the Lewis acid adducts increase in the following order: tetrahydrofuran, pyridine, and tetramethylethylenediamine.

The molar ratio of Group IIA metal and transition metal carbonyl complex is preferably greater than 1, since traces of oxygen will cause oxidation of the Group IIA-transition metal carbonyl complex according to the following reaction:

B_x Me(M)₂ + 1/2 O₂ → xB + MeO + M-M

wherein the symbols have the meanings ascribed previously.

If the Group IIA metal is in excess, it will convert the transition metal carbonyl dimer back to the desired product according to the following reaction:

M-M + Me (B) B_x Me[M]₂

the MeO is easily separable since it will usually be a filterable solid. Also, if the transition metal carbonyl complex is in excess, the unreacted portion will be difficult to remove from the desired Group IIA-transition metal carbonyl compound.

For the above reasons, the mole ratio of Group IIA metal to transition metal usually ranges from 1 to 100 with a range of 1.1 to 10 preferred, and 1.1 to 3.3 especially preferred. It should be noted that if one does not intend to isolate the product, or does not find the economics, of separating the desired products from the reactants, unattractive, lower ratios may be used.

The novel compounds described herein may be used as a catalyst in a variety of chemical processes in addition to the ether forming process. For example, unsaturated organic compounds can be hydrogenated to give the corresponding saturated derivatives. This catalyst is also useful for hydroformylation reactions wherein an alkene is reacted with carbon monoxide and hydrogen to form aldehydes and alcohols. Excellent selectivity has been shown by the tetrakis tetrahydrofuran adduct of a magnesium-dicobalt hexacarbonyl bis-methyldiphenylphosphine in the conversion of 1-hexene to heptaldehydes. The conversion was >99% with a selectivity of 87%. This conversion is run at elevated pressure, preferably from 1,500 to 3,000 psi. Reaction temperatures will range from 50°C to 200°C, with a range of 100°C to 150°C preferred. Ratio of H₂ to CO used will vary with reaction conditions; preferably a 1 to 1 ratio is maintained. The catalyst concentration will range from 0.01 to 20% based on the weight feed, with 0.05 to 10% preferred.

The novel compounds described herein have also shown utility in the preparation of cyclic dimers and trimers of butadiene. In particular, cyclododecatriene may be produced by the trimerization of butadiene.

The above uses are in addition to the formation of ethers from alkanol by use of the novel catalysts described above.

Reactions which utilize the novel catalyst will usually be run in the liquid phase; i.e., one advantageous characteristic of the catalyst of this invention is that its solubility in organic solvents can be varied by the proper choice of Lewis base adduct, thereby allowing the skilled artist to design a homogeneous or heterogeneous catalyst system. The reactions which utilize the novel catalyst will be run at temperatures ranging from -50°C to 500°C and pressures ranging from subatmospheric to superatmospheric, according to the specific reaction. The proper temperatures and pressure conditions will be apparent to one skilled in the art. In a like manner, the reaction times and the catalyst concentrations will vary according to the specific reaction, and will also be apparent to the skilled artist.

The following examples serve to more fully describe, the manner of making and using the above-described invention, as well as to set forth the best modes contemplated for carrying out various aspects of the invention. It is understood that these examples in no way serve to limit the true scope of this invention, but rather, are presented for illustrative purposes.

Preparation of the Novel Catalyst

In the preparation of the novel catalyst, all reactions were carried out under a nitrogen atmosphere.

EXAMPLE A

PAC Preparation of [C₄ H₈ O]₂ Mg[Fe(CO)₂ C₅ H₅ ]₂

Method (1)

0.2 gms. MgBr₂ dissolved in 15 mls. of tetrahydrofuran was added dropwise to a solution of 0.4 gms. NaFe(CO)₂ C₅ H₅ in 30 ml. of tetrahydrofuran, in a 100 ml. flask equipped with a magnetic stirrer. The NaFe(CO)₂ C₅ H₅ had been prepared by the reductive cleavage of [C₅ H₅ Fe(CO)₂ ]₂ with 1% sodium amalgam. This mixture was allowed to stir at room temperature for 24 hours. The crude reaction mixture was filtered with reduced pressure to remove the insoluble salts formed during the reaction. The filtrate was concentrated with reduced pressure. The concentrate was slowly poured into n-pentane which affected the precipitation of a yellow-orange solid. The crude product was recrystallized several times from benzene and vacuum dried. The pure solid is a bright yellow solid and is extremely air sensitive. Upon atmospheric exposure the magnesium-transition metal compound is quantitatively oxidized to [C₅ H₅ Fe (CO)₂ ]₂ and MgO. The stoichiometry of the complex was established by nmr and elemental analyses. The composition of all of the following novel products were determined by a combination of nmr and elemental analysis.

Calculated for [C₄ H₈ O]₂ Mg[Fe(CO)₂ C₅ H₅ ]₂ ; 50.5% C, 4.97% H, 4.59% Mg, 21.6% Fe and a molecular weight of 522.

Found for reaction product: 46.7% C, 4.83% H, 4.64% Mg, 22.5% Fe and a molecular weight of 528 in benzene.

Elemental analyses, molecular weight and color data for the novel catalyst compounds synthesized in this example and following examples are given in Table I.

It should be noted that the halide intermediates postulated by Burlich and Ulmer were not produced.

TABLE I
ANALYTICAL DATA, MOLECULAR WEIGHTS(a) AND COLORS   Molecular
Calculated % Found % Weight Compound Color C H Mg Me1 P N C H Mg
Me' P N Calc. Found
(THF)2 Mg(Fe(CO)2 C5 H5)2 Yellow 50.5 4.97
4.59 21.6 -- -- 46.7 4.83 4.64 22.5 -- --  522 528 (Pyridine)2
Mg[Fe(CO)2 C5 H5 ]2 Yellow 53.6 3.74 4.54 20.8 --
5.24 54.9 5.16 4.82 17.7 -- 5.76  536 498 (THF)4 Mg[Mo(CO)2
PCH3 (C6 H5)2 C5 H5 ]2 Light 58.6
5.83 2.10 16.8 5.41 -- 58.3 5.61 3.09 17.4 6.25 -- -- --  Yellow
(THF)4 Mg[Mo(CO)2 P(C4 H9)3 C5 H5
]2 Yellow 56.4 8.35 2.11 16.7 5.39 -- 55.9 8.37 2.37 18.1 5.51 --
1150 599 (Pyridine)4 Mg[Co(CO)4 ]2 Yellow 49.3 2.96 3.42
17.3 -- 8.22 49.4 3.26 2.91 17.1 -- 7.79  682 665 (THF)4
Mg[Co(CO)3 PCH3 (C6 H5)2 ]2 Yellow 57.6
5.83 2.40 11.8 6.20 -- 55.9 6.01 2.36 11.1 6.26 -- -- --  Yellow
(THF)4 Mg[Co(CO)3 P(C4 H9)3 ]2 Green 55.2
8.60 2.43 11.8 6.20 -- 54.6 8.74 2.45 11.4 5.99 -- 1002 310 (Pyridine).su
b.4 Mg[Co(CO)3 PCH3 (C6 H5)2 ]2 Yellow
60.6 4.48 2.38 11.6 5.99 5.46 58.6 4.51 2.51 11.7 5.69 5.41 -- --
(TMEDA)2 Mg[Co(CO)3 PCH3 (C6 H5)2 ]2
Yellow 56.1 6.15 2.58 12.5 -- -- 53.5 6.14 2.66 12.9 -- -- -- --
(THF)4 Mg(Mn(CO)5)2 Yellow 44.5 4.56 3.46 15.7 -- -- 43.7
5.26 3.91 13.6 -- -- -- -- (THF)4 Mg[Mn(CO)4 PCH3
(C6 H5)2 ]2 Yellow 57.4 5.54 2.32 10.5 5.94 -- 56.6
6.01 2.55 9.79 6.19 -- -- -- (Pyridine)4 Mg[Mn(CO)5 ]2
Light 49.3 2.94 3.29 15.1 -- 7.67 47.6 3.11 2.91 14.9 -- 7.72 -- --
Green (THF)2 Mg[Rh(CO)2 (P(C6 H5)3)2
]2 Orange -- -- 1.58 13.4 -- -- -- -- 1.34 14.3 -- -- -- --
(a) Molecular weights were determined cryoscopically employing
benzene solutions.

Method (2)

A solution containing 5.5 gm of Hg[Fe(CO)₂ C₅ H₅ ]₂ in 75 ml. of tetrahydrofuran was added to a heavy walled reaction tube (equipped with a teflon vacuum stopcock) containing 0.5 gm of 200 mesh magnesium metal. The metal and reaction tube had previously been flamed out under a vacuum of 10-4 mm. The reaction tube was sealed under vacuum and placed in an oil bath held at 85°C After 24 hours the tube was broken and the contents filtered. The filtrate was concentrated with reduced pressure. The concentrate was poured into n-pentane which caused the precipitation of a yellow solid. The solid was collected and washed several times with a 25:75 mixture of benzene and n-pentane to remove any unreacted Hg[Fe(CO)₂ C₅ H₅ ]₂. The final purification procedure was recrystallization from benzene. The yield was 4.2 gm. of [C₄ H₈ O]₂ Mg[Fe(CO)₂ C₅ H₅ ]₂.

Method (3)

1.0 gm. of magnesium powder (200 mesh) was placed in a heavy wall reaction tube. The tube and its contents were flamed out at 10-4 mm. A solution of 6.0 gm. of C₅ H₅ Fe(CO)₂ I in 75 ml. of tetrahydrofuran was placed in the reaction tube. After a short induction period the reaction became exothermic enough to warm tetrahydrofuran to its reflux point. The initial red solution quickly turned dark yellow and the reaction appeared complete in 15 or 20 minutes. The crude reaction mixture was filtered. MgI₂ was collected on the filter and discarded. The filtrate was concentrated with reduced pressure. The concentrate was flooded with n-pentane causing the immediate precipitation of a yellow solid. The crude reaction product was collected and washed with a 50:50 mixture of n-pentane-ether to remove any unreacted C₅ H₅ Fe(CO)₂ I. The remaining yellow solid was then recrystallized several times from benzene. The yield was very nearly quantitative.

Method (4)

In a 250 ml, 1-neck, round bottom flask 50 gm. of mercury and 0.6 gm. of 200 mesh magnesium powder were rapidly stirred to form the amalgam. The amalgam was allowed to cool to room temperature. To the amalgam was added a solution containing 5.0 gm. of [C₅ H₅ Fe(CO)₂ ]₂ in 75 ml of tetrahydrofuran. The resulting solution was deep red. The flask was stoppered and the mixture was stirred vigorously. After 18 hours the solution had become a yellow-green. The reaction mixture was filtered to free it from the amalgam. The filtrate was concentrated with reduced pressure to approximately 25 ml. The concentrated tetrahydrofuran solution was flooded with n-pentane, yielding a yellow solid. The yellow solid was recrystallized from benzene and vacuum dried. The yield was 7.2 gm. of [C₄ H₈ O]₂ Mg[Fe(CO)₂ C₅ H₅ ]₂.

EXAMPLE B

PAC Preparation of (C₅ H₅ N)₂ Mg[Fe(CO)₂ C₅ H₅ ]₂

In a 250 ml., 1-neck round bottom flask an amalgam consisting of 50 gm. of mercury and 0.6 gm. of powdered magnesium (200 mesh) was prepared. A solution containing 6.7 gm. of pyridine in 125 ml. of benzene was added to the flask. To the benzene-pyridine solution was added 5.0 gm. of [C₅ H₅ Fe(CO)₂ ]₂. The resultant solution was deep red. After 18 hours the solution had become a reddish-yellow with a considerable amount of a yellow solid suspended in the solution. The reaction mixture was filtered and an orange-yellow solid was collected. The collected solid was taken up in benzene and filtered to free it of magnesium amalgam. The filtrate was concentrated with reduced pressure. The concentrate was flooded with n-pentane, knocking out of solution a bright yellow solid. The solid was recrystallized from benzene and then vacuum dried. The yield was nearly quantitative. The bright yellow solid is air sensitive and is quantitatively oxidized to [C₅ H₅ Fe(CO)₂ ]₂ and MgO upon exposure to the air. The stoichiometry of the complex was established by nmr measurements and elemental analysis.

EXAMPLE C

PAC Preparation of (C₄ H₈ O)₄ Mg[Mo(CO)₃ C₅ H₅ ]₂

This compound was prepared by a method similar to that used in the preparation of [C₄ H₈ O]₂ Mg[Fe(CO)₂ C₅ H₅ ]₂ described in Method 3 of Example A. C₅ H₅ Mo(CO)₃ I was prepared by cleaving the molybdenum-molybdenum bond of [Mo(CO)₃ C₅ H₅ ]₂ with I₂ in tetrahydrofuran solution. The magnesium-molybdenum compound is white and is only sparingly soluble in tetrahydrofuran. The stoichiometry of the compound (C₄ H₈ O)₄ Mg[Mo(CO)₃ C₅ H₅ ]₂ was established by nmr measurements (solutions in d-acetonitrile) and elemental analysis. The same product was also prepared by cleaving (Mo(CO)₃ C₅ H₅)₂ with magnesium amalgam in tetrahydrofuran solution.

EXAMPLE D

PAC Preparation of (C₅ H₅ N)₄ Mg[Mo(CO)₃ C₅ H₅ ]₂

This compound was prepared by a method similar to that used in the preparation of the pyridine adduct, (C₅ H₅ N)₂ Mg[Fe(CO)₂ C₅ H₅ ]₂, described in Method 4 of Example A. The molybdenum cyclopentadienyl tricarbonyl dimer, [C₅ H₅ Mo(CO)₃ ]₂, was cleaved with magnesium amalgam in benzene solution in the presence of excess pyridine. The solubility of (C₅ H₅ N)₄ Mg[Mo(CO)₃ C₅ H₅ ]₂ in benzene was found to be greater than the tetrakis tetrahydrofuran adduct. The pure solid is a light green. The stoichiometry of the compound was determined by nmr measurements upon d-acetonitrile solutions.

EXAMPLE E

PAC Preparation of (C₄ H₈ O)₄ Mg[Mo(CO)₂ (PCH₃ (C₆ H₅)₂)C₅ H₅ ]₂

0.2 gm. of magnesium powder (200 mesh) was flamed out in a heavy walled reaction tube (equipped with a teflon stopcock) under a vacuum of 10-4 mm. A solution containing 4.0 gm. of C₅ H₅ Mo(CO)₂ (CH₃ P(C₆ H₅)₂)I (prepared by reacting equimolar quantities of C₅ H₅ Mo(CO)₃ I and CH₃ P(C₆ H₅)₂ in benzene solution) in 25 ml. of tetrahydrofuran was added to the reaction tube. The stopcock was closed and the tube was placed in an oil bath held at 50°C to 60°C After 18 hours the bulk of the magnesium powder had been consumed and an off-white solid had come out of solution. The vessel's contents were filtered leaving MgI₂ on the frit. The filtrate was concentrated with reduced pressure. A yellow solid was obtained by flooding the tetrahydrofuran concentrate with n-pentane. This solid was washed with a 50:50 mixture of benzene and n-pentane to remove any unreacted starting material. Nmr and elemental analysis have shown this compound to be the tetrakis tetrahydrofuran adduct. The tetrakis tetrahydrofuran adduct was also obtained in good yield by substituting a magnesium amalgam for the magnesium powder. The amalgam reaction was carried out at room temperature.

EXAMPLE F

PAC Preparation of (C₄ H₈ O)₄ Mg[Co(CO)₄ ]₂

This compound was prepared by cleaving the cobalt-cobalt bond in Co₂ (CO)₈ with magnesium amalgam in tetrahydrofuran solution. The dark yellow product is extremely air sensitive and is sparingly soluble in common organic solvents. The air oxidation products are MgO and Co₂ (CO)₈. The compound's low solubility would not allow a recrystallization, so purification was effected by repeated washings with a 50:50 tetrahydrofuran-n-pentane mixture. The washed solid was extracted with tetrahydrofuran yielding a dark yellow solution (solubility ca. 1 gm/l). A dark yellow solid was isolated by adding n-pentane to the saturated tetrahydrofuran solution. Infrared measurements showed the compound to be free of impurities.

EXAMPLE G

PAC Preparation of (C₅ H₅ N)₄ Mg[Co(CO)₄ ]₂

This compound was prepared by cleaving Co₂ (CO)₈ with magnesium amalgam in the presence of excess pyridine in benzene solution. The compound exhibits good solubility in hydrocarbon solvents and was recrystallized from benzene. Elemental analysis confirmed the preparation of the tetrakis pyridine adduct. The analytically pure compound is air light yellow. The compound is air sensitive but less so than (C₄ H₈ O)₄ Mg[Co(CO)₄ ]₂.

EXAMPLE H

PAC Preparation of (C₄ H₈ O)₄ Mg[Co(CO)₃ PCH₃ (C₆ H₅)₂ ]₂

This compound was prepared by cleaving the cobalt-cobalt bond in Co₂ (CO)₆ (CH₃ P(C₆ H₅)₂)₂ with magnesium amalgam in tetrahydrofuran solution. Co₂ (CO)₆ (CH₃ P(C₆ H₅)₂)₂ was prepared by allowing two equivalents of CH₃ P(C₆ H₅)₂ to react with one equivalent of Co₂ (CO)₈ in refluxing benzene. The substitution reaction was complete in 24 hours. (C₄ H₈ O)₄ Mg [Co(CO)₃ CH₃ P(C₆ H₅)₂ ]₂ was obtained analytically pure by repeated recrystallizations from benzene. The pure compound is yellow. The stoichiometry of the compound was established by elemental analyses and nmr measurements.

EXAMPLE I

PAC Preparation of (C₅ H₅ N)₄ Mg[Co(CO)₃ PCH₃ (C₆ H₅)₂ ]₂

This was prepared by reducing a benzene solution of Co₂ (CO)₆ (PCH₃ (C₆ H₅)₂)₂ with magnesium amalgam in the presence of a two-fold excess of pyridine. A light yellow, air sensitive solid was isolated by concentrating the filtered reaction mixture with reduced pressure and flooding the concentrate with n-pentane. The product was purified by recrystallizing from benzene. The yield was nearly 100%. The molecular formula was obtained by nmr measurements and elemental analyses.

EXAMPLE J

PAC Preparation of [(CH₃)₂ NCH₂ CH₂ N(CH₃)₂ ]₂ Mg[Co(CO)₃ PCH₃ (C₆ H₅)₂ ]₂

This light yellow compound was obtained in a manner very similar to that used in preparing (C₅ H₅ N)₄ Mg[Co(CO)₃ PCH₃ (C₆ H₅)₂ ]₂ but with tetramethylethylenediamine (TMEDA) being substituted for pyridine. The stoichiometry of the compound was established by elemental analyses and nmr measurements.

EXAMPLE K

PAC Preparation of (C₄ H₈ O)₄ Mg[Mn(CO)₂ ]₂

A 0.1 molar solution of Mn₂ (CO)₁0 in tetrahydrofuran was reduced with excess 1% magnesium amalgam. After 18 hours the reaction mixture was filtered and a yellow filtrate was obtained. The filtrate was concentrated with reduced pressure. The concentrate yielded a yellow solid upon addition of n-pentane. The air sensitive yellow solid was found to be only sparingly soluble in benzene. Purification was effected by washing the solid with a 50:50 benzene-n-pentane mixture to remove any unreacted Mn₂ (CO)₁0. The washed solid was redissolved in tetrahydrofuran, filtered and reprecipitated with n-pentane. This redissolving-reprecipitation process was repeated several times. The yield was very nearly quantitative. Elemental analysis established the compound as the tetrakis tetrahydrofuran adduct. Note that the elemental analysis (Table I) establishes that the bis-adduct is not formed, as claimed by Hieber et al. Infrared spectral studies also confirm that the tetrakis adduct is the only product formed.

EXAMPLE L

PAC Preparation of (C₄ H₈ 0)₄ Mg[Mn(CO)₄ PCH₃ (C₆ H₅)₂ ]₂

To a slurry of (C₄ H₈ O)₄ Mg(Mn(CO)₅)₂ in toluene a two molar equivalent of CH₃ P(C₆ H₅)₂ was added and the mixture was refluxed for two hours. While concentrating the reaction mixture with reduced pressure, a yellow solid came out of solution and was collected by filtration. The stoichiometry of the phosphine derivative was established by elemental analysis and nmr spectroscopy. The addition of phosphine was nearly quantitative. The phosphine derivative has much better solubility in aromatic solvents than the unsubstituted compound.

EXAMPLE M

PAC Preparation of (C₅ H₅ N)₄ Mg[Mn(CO)₅ ]₂

A 0.1 molar solution of Mn₂ (CO)₁0 in benzene containing a small stoichiometric excess of pyridine was reduced with a 1% magnesium amalgam. After 18 hours the reaction mixture was filtered yielding a light green filtrate. Solvent was removed from the filtrate until solid started to come out of solution. N-pentane was added to the concentrated solution, resulting in a nearly quantitative recovery of the desired product. The recrystallized compound is light green. The stoichiometry of the air compound was established by elemental analysis.

Use of the Novel Catalyst in the Preparation of Ethers

PAC EXAMPLE 1 - Preparation of Dimethyl Ether

A 300 ml autoclave was used for all of the following alcohol carbonylation runs. All solution preparations were carried out in an inert (i.e., nitrogen) atmosphere enclosure. The reaction products were analyzed by standard gas-liquid chromatography procedures.

______________________________________
(C4 H8 O)4 *Mg[Mn(CO)5 ]2 + CH3 I catalyst
system
Feed: 2.0 gm(2.8 mmoles) (C4 H8 O)4 Mg[Mn(CO)5
]2
3.0 ml (48 mmoles) CH3 I
30 ml methanol
70 ml benzene
Reaction conditions: 500 psig CO pressure
150°C
20 hours
Products: 95% conversion to CH3 OCH3, trace amount
of methyl acetate
______________________________________
* = tetrahydrofuran (THF)?

EXAMPLE 2 -- Use of Molybdenum Containing Catalyst for the Preparation of Dimethyl Ether

______________________________________
(C4 H8 O)4 Mg[Mo(CO)2 (C5 H5)P(C4
H9)3 ]2 + CH3 I
catalyst system
Feed: 2.0 gm (1.7 mmoles)
(C4 H8 O)4 Mg[Mo(CO)2 C5 H5)P(C4
H9)3 ]2
1.0 ml. (16 mmoles) CH3 I
30 ml methanol
70 ml benzene
Reaction conditions: 400 psig CO pressure
180°C
70 hours
Products: 95% conversion to CH3 OCH3, trace amount
of methyl acetate.
______________________________________

EXAMPLE 3 -- Use of Cobalt Containing Catalyst for the Preparation of Dimethyl Ether

______________________________________
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2 + CH3 I
catalyst system
Feed: 2.0 gm (2 mmoles)
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2
1.0 ml (16 mmoles) CH3 I
30 ml methanol
70 ml benzene
Reaction conditions: 300 psig CO pressure
180° C
72 hours
Products: 80% conversion to CH3 OCH3, trace amount
of methyl acetate
______________________________________

It is to be noted that in Examples 2 and 3 a cocatalyst to catalyst ratio of more than 8 resulted in almost total conversion to ether, with only trace amounts of the ester.

EXAMPLE 4 -- Carbonylation of Ethanol

______________________________________
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2 + CH3 I
catalyst system
Feed: 2.0 gm (2 mmoles)
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2
0.5 ml (8 mmoles) CH3 I
100 ml ethanol
Reaction conditions: 600 psig CO pressure
200°C
48 hours
Products: 15% conversion to ethyl propionate
6.7% conversion to ethyl ether
______________________________________

EXAMPLE 5 -- Mixed Alcohol Carbonylation Process

______________________________________
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2 + CH3 I
catalyst system
Feed: 0.5 gm (0.5 mmoles)
(C4 H8 O)4 Mg[Co(CO)3 P(C4 H9)3
]2
0.5 ml (8 mmoles) CH3 I
30 ml isopropanol
40 ml benzene
30 ml methanol
Reaction conditions: 800 psig CO pressure
185°C
72 hours
Products: wt. %, methanol 1, isopropanol 20,
methyl acetate 15, isoproyl acetate 25,
diisopropyl ether 5, methyl isopropyl
ether 20, dimethyl ether 5.
______________________________________

Example 5 is typical of mixed alcohol runs where unsymmetrical ethers and lower alcohol acyl esters are preferentially formed. CH₃ I/catalyst ratios higher than 16 would give nearly exclusively ether products with the asymmetric ether product predominating.

EXAMPLE 6 -- Conversion of Methyl Alcohol to Dimethyl Ether

In a series of experiments methyl alcohol was dehydrated in the presence of Group IIA metal-Group VI, VII and Group VIII metal catalyst systems. The catalyst systems, the reaction conditions and the results of these experiments are summarized in Table II. The table shows that upon increasing the CH₃ I/catalyst mole ratio above 8 a very good conversion and selectivity to dimethyl ether occurs. At lower ratios the Mg-Co catalyst system exhibited good conversion and selectivity to methyl acetate. It should be further noted that the production of the ether is enhanced at low CO partial pressures. A certain CO pressure (about 200-300 psig) is required, however, to maintain catalyst integrity.

TABLE II
__________________________________________________________________________
DEHYDRATION OF METHANOL TO DIMETHYL ETHER(a)
CH3 I
CO  t  % Conv. to
% Selectivity
Catalyst    mmole
(mmole)
(psig)
(hr)
CH3 OCH3
to CH3 OCH3(b)
__________________________________________________________________________
(THF)4 Mg[Mn(CO)5 ]2
2.8 8.0  1000
19 Trace  --
"       2.8 16   1000
18 40     99
"       2.8 48    500
20 99     99
(THF)4 Mg[Mn(CO)4
2.8 48    500
20 99     99
(P(C4 H9))]2
(THF)4 Mg[Mo(CO)2
1.7 16    400
70 99     99
(C5 H5)(P(C4 H9)3)]2
(THF)4 Mg[Co(CO)3
2.0 8.0  1000
19 Trace  --
P(C4 H9)3)]2
"       2.0 16.0 1000
24   1.8    8.0
"       2.0 16.0  300
72 80     99
"       2.0 32   1000
18 62     99
"       2.0 48   1000
18 99     99
__________________________________________________________________________
(a) Feedstock 90 ml CH3 OH (2.22 moles), 10 ml benzene (0.11
moles) carbonylation and dehydration carried out at 175°C
(b) Major additional product is methylacetate. For practical purpose
conversion and selectivities of 99% are quantitative production of
CH3 OCH3.

While the invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modification, and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice in the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as fall within the scope of the invention.

Claims

1. A process for the preparation of ethers which comprises:

(A) contacting carbon monoxide with at least one C₁ to C₂0 alkanol at a temperature in the range from about 150° to about 400°C and at a carbon monoxide partial pressure in the range from about 200 to about 1000 psig in the presence of a catalyst system having the general formula:

b_x Me[Me'(CO)_a (L)_b ]₂

and an iodine containing cocatalyst in cocatalyst to catalyst molar ratio ranging from about 16 to about 100, wherein b is a lewis base capable of coordinating with a group iia metal, Me' is a transition metal selected from the group consisting of metals of Groups VIB and VIIB and VIII of the Periodic Table of Elements, Me is a group iia metal, L is a uni- or polydentate ligand or hydrocarbon capable of coordinating with said transition metal; x is a positive integer ranging from 1 to 4; a is a positive integer ranging from 1 to 5 and b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less; and

(b) obtaining at least one ether reaction product from said process.

2. The process of claim 1 wherein the iodine containing cocatalyst is a member selected from the group consisting of I₂, HI and organo iodides.

3. The process of claim 1 wherein the lewis base is a member selected from the group consisting of tetrahydrofuran, pyridine and tetramethylethylenediamine.

4. The process of claim 1 wherein Me' is manganese.

5. The process of claim 1 wherein Me is magnesium.

6. The process of claim 1 wherein L is a member selected from the group consisting of compounds of the general formulae: ##STR11## wherein R, R', R" and R'" are hydrocarbyl radicals independently selected from the group consisting of hydrogen, C₁ to C₂0 alkyl, C₃ to C₂0 cycloalkyl, C₆ to C₂0 aryl and C₇ to C₂0 aralkyl and alkaryl radicals.

7. The process of claim 1 wherein the catalyst system is represented by the formula:

(C₄ H₈ O)₄ Mg[Mn(CO)₃ ]₂

8. The process of claim 1 wherein the alkanol is selected from the group consisting of methanol, ethanol, propanol, butanol and mixtures thereof.

9. The process of claim 1 wherein the catalyst system is represented by the formula:

(C₄ H₈ O)₄ Mg[Mn(CO)₄ P(C₄ H₉)₂ ]₂

the iodine containing cocatalyst is CH₃ I in a cocatalyst to catalyst molar ratio ranging from 16 to 100 and the alkanol is methanol.

10. A process for the production of ethers which comprises:

(A) contacting carbon monoxide with at least one C₁ to C₂0 alkanol at a temperature in the range from about 150° to 400°C and at a pressure in the range from about 200 to about 1000 psig in the presence of a catalyst system having the general formula:

b_x Me[Me'(CO)_a (L)_b ]₂

and an iodine containing cocatalyst, wherein the molar ratio of cocatalyst to catalyst ranges from about 16 to 100, wherein b is a lewis base capable of coordinating with a group iia metal and being a member selected from the group consisting of:

(1) organic nitrogen bases selected from the group consisting of:

(a) monofunctional nitrogenous bases represented by the general formulae: ##STR12## wherein R, R' and R" are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals;

(b) polyfunctional nitrogenous bases represented by the general formula: ##STR13## wherein R'" and Rⁱv are selected from the group consisting of hydrogen and C₁ to C₁0 hydrocarbyl radicals, R₁ is selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals, Z is selected from the group consisting of radicals represented by the general formulae: ##STR14## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals and y is a positive integer of from 1 to 3;

(c) heteroring nitrogenous bases selected from the group consisting of piperazine, pyrrolidine, pyridine and substituted pyridines of the formula: ##STR15## wherein R₆ is a C₁ to C₁0 hydrocarbyl radical and z is an integer from 0 to 5; and

(2) ethers selected from the group consisting of:

(a) monofunctional ethers represented by the general formula:

R -- O -- R'

wherein R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0, C₇ to C₁0 alkaryl and aralkyl radicals;

(b) polyfunctional ethers represented by the general formulae: ##STR16## wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals, R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₆ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals and y is a positive integer of from 1 to 3;

(c) cyclic ethers selected from the group consisting of tetrahydrofuran and dioxane;

(3) ketones represented by the general formula: ##STR17## where R and R' are hydrocarbyl radicals independently selected from the group consisting of C₁ to C₁0 alkyl, C₃ to C₁0 cycloalkyl, C₂ to C₁0 aryl and C₇ to C₁0 alkaryl and aralkyl radicals, R₁ and R₂ are independently selected from the group consisting of hydrogen and C₁ to C₄ alkyl radicals and z is an integer of from 0 to 3;

Me is a group iia metal;

Me' is a transition metal selected from the group consisting of metals of Groups VIB, VIIB, and VIII of the Periodic Table of the Elements;

x is a positive integer from 1 to 4;

a is a positive integer ranging from 1 to 5;

b is an integer ranging from 0 to 4, with the proviso that the sum of a and b is 5 or less;

L is a uni- or polydentate ligand capable of coordinating with the transition metal or a hydrocarbon residue which is selected from the group consisting of compounds of the following general formula: ##STR18## wherein R, R', R" and R'" are hydrocarbyl radicals independently selected from the group consisting of hydrogen, C₁ to C₂0 alkyl, C₃ to C₂0 cycloalkyl, C₆ to C₂0 aryl, and C₇ to C₂0 aralkyl and alkaryl radicals; and

X is selected from the group consisting of N, P, As and Sb, wherein said catalyst system includes an iodine containing cocatalyst, wherein the molar ratio of cocatalyst to catalyst ranges from about 16 to 100; and

(b) obtaining at least one ether reaction product from said process.

11. The process of claim 10 wherein Me is magnesium.

12. The process of claim 10 wherein Me' is selected from the group consisting of manganese, molybdenum and cobalt.

13. A process for the preparation of dimethylether which comprises:

(A) contacting carbon monoxide with methyl alcohol at a temperature in the range from about 150° to about 400°C at a carbon monoxide partial pressure in the range from about 200 psig to about 1000 psig in the presence of a catalyst system having the formula selected from the group consisting of:

(C₄ H₈ O)₄ Mg[Mn(CO)₅ ]₂ ;

(C₄ H₈ O)₄ Mg[Mn(CO)₄ (P(C₄ H₉))]₂ ;

(C₄ H₈ O)₄ Mg[Mo(CO₂)(C₅ H₅)(P(C₄ H₉)₃)]₂ ; and

(C₄ H₈ O)Mg[Co(CO)₃ P(C₄ H₉)₃ ]₂

and a cocatalyst consisting essentially of methyl iodide in a cocatalyst to catalyst molar ratio ranging from 16 to 100; and

(b) obtaining dimethylether from said process.

14. The process of claim 13 wherein the process is carried out at a temperature of about 175°C and at a carbon monoxide partial pressure of about 500 psig.